Polyazodyestuffs



Patented May 20, 1941 mreo STATES POLYAZODYESTUFFS Detlef Delfs and Eberhard Stein, Leverkusen-I.

G.-Werk, Germany, assignors to General Aniline & Film Corporation, a corporation of Delaware No Drawing. Application March 7, 1939, Serial No. 260,341. In Germany March 11, 1938 15 Claims.

The present invention relates to new polyazodyestuiis and to a process of preparing the same, more particularly it relates to polyazodyestuffs of the following general formula:

I O.Rs.OOOH

In this formula R1-N:N- stands for the radical of any diazo compound, -O.R3OOOH stands for the radical of a hydroxy-carboxylic acid, the hydroxy group of which stands in aor B-position to the COOH-group, R4 stands for the radical of a coupling component bearing a. hydroxy group in a position adjacent to the N=N- bridge, R2 may be further substituted and at least one of the radicals R1 and R4 is substituted by an arylazo radical.

The new dyestuffs are obtained by coupling SIOaH SOaH the diazo compounds of amino-azodyestuffs of the general formula:

H: (i) 3H The following examples illustrate the invention without, however, limiting it thereto, the parts being by weight.

Example 1 A hydrochloric diazo solution correspondin to 6.9 parts of sodium nitrite is prepared of the aminoazodyestufi which is obtained by condiazotized 2-aminonaphthalene-4.8-disulfonic acid with m-toluidine, subsequently diazotizing and coupling with 4-methy1-2-aminophenoxyacetic acid. To this solution there is added at 5 C. with stirring the solution of 37.8 parts of the dyestufi, which is obtained by an acid coupling of diazotized aminotriazole-carboxylic acid with 2-amino-5-hydroxynaphtha1ene-7-su1fonic acid, and 85 parts of anhydrous sodium carbonate in 1400 parts of water, keeping the mixture sodium carbonate alkaline during the coupling. When the coupling is complete the dyestufi is salted out. It corresponds in the free state to the following formula:

and dyes cotton blue-grey shades; the dyeing aftertreated with :copper salts is grey.

Example 2 A suspension of the diazo compound corresponding to 6.9 parts of sodium nitrite is prepared of the dyestuff which is obtained by coupling diazotized 2-aminonaphthalene-4.8-disulfonic acid with m-toluidine, diazotizing and coupling with m-toluidine again diazotizing and coupling with 4-methy1-2-amlnophenoxy-acetic acid. To this suspension there is added at 5 C. with stirring the solution of 32 parts of Z-phenylamino 8 hydroxynaphthalene-6-sulfonic acid and 25 parts of anhydrous sodium carbonate in 1000 parts of water, keeping the mixture sodium carbonate alkaline during the coupling. When sodium carbonate in 900 parts of water, keeping the coupling is complete the dyestufi is isolated the mixture sodium carbonate alkaline during in the usual way; it dyes cotton grey-brown the coupling. The dyestufl which is isolated in shades, the dyeing aftertreated with copper salts the usual way after the coupling is complete is brown. In its free state the dyestufi correyields on cotton reddish-grey, when aftertreatsponds to the following formula: ed with copper salts dark grey shades. The dye- H033 301K $H3 C =NQN=NQN=NQN=N Ha H: H

' cHicooH SOaH If 2-phenylamino-8-hydroxynaphthalene-6- stufi corresponds in its free state to the followsulfonic acid is replaced by 2-phenylamino-5- ing formula:

HOaS (13H:

oniooon hydroxvnaphthalene- 'l-sulfonio acid-or -by the If 2-phenylamino-5-hydroxy-7-sulfonic acid is azo dyestufi obtained from diazotized aminoreplaced by the coupling components mentioned triazole-carboxylic acid and 2-amino-5-hydroxyin the following table, dyestufis are obtained, naphthalene-'l-sulfonic acid in acid medium dyeing cotton shades as indicated.

dyestuffs are obtained, dyeing cotton grey-blue shades. By aftertreatment with copper salts I Dyeing on Dyeing on grey-green to olive-grey shades are obtained. Coupling n p n nt comm tvoifllhizlggfptgfggigs Example? j I v z-amino-5;hydroxynaphtlialene- Currant Dark-grcy-black. There is prepared an aqueous suspension of 2- a sn 8 h yfioxynaphthalene- Greenish dark- Black brown. the diazo compound of the dyestuif (quantity fiulfonicgacid. grey. 7 corresponding to 6.9 parts of sodium nitrite), gggg ggggggggggggy ,Bwwnwhich is bt i d b u li g djaz tjz d p- 1-(4.8-disnlfo-2'-nephthyl)-3- Orongebrown. Orange brown. aminobenzene-azo l ylic acid with 4-methylz-t i efi z o y lfn rim l i ygoxynaph Currant .4. Violet brown. Z-aminophenoxy-aoetic acid. To this suspenthelefleq-sulfollic e sion there is added at 5 0. with stirring the gtggg' ggmggw g ggfifiiiif; 35. 3p solution of 32 parts of 2r-phenylamino-5-hydroxyg i fizg g naphthalene-'T-sulfonic acid and 25 parts off igfi ifig iflg git fgfij anhydrous sodium carbonate in 950 parts of ionic Midinacid mediumwater, keeping the mixture sodium carbonate alkaline during the coupling. The isolated dye- If instead of the above employed diazo comstufi yields on cotton blue-grey shades and when pound the diazo compound of the dyestufl's obert e te W opp S s dark grey shades. tained bycoupling diazotized 4-aminobenzoyl-4- The dyestufi corresponds in its free state to the aminobenzene-azo-salicylic acid with 4-methoxyfollowing formula: Z-amino-phenoXy-acetic acid or with aor 3-(4- HO S CHLCOOH 7 Example 4 7 methyl amino-phenoxy) propionic acid is There prepared a suspension of the diazo coupled in analogous manner with 2-phenylcompound of the dyestufi (quantity correspon amino-5-hydroxynaphthalene 7 sulfonic acid ing to 6.9 parts of sodium nitrite) which is ob- H dyestuffs are Qbtained which dye cotton when tained by coupling of diazotized 4-aminobenzoylaftertreated Wlth copper salts blue-grey 0 dark 4-aminobenzene-azo-salicylic acid with i-methylgrey shades- 2-aminophenoxy-acetic acid. To the suspension Example 5 there is added a 5 C. with stirring the solution of V i 4 32 parts of 2-phenylamino-5-hydroxynaphtha- The suspension of the diazo compound of the lene-7-sulfonic acid and 85 parts. of anhydrous dyestuff of the constitution:

I I I coon soan Hogs 0.0Hz.COOH

mentioned coupling component is replaced by other coupling components 10 Dyeing on Coupling component gggg ggggg gg copper salts 1 z-lphegyllaliglino-c ;1hydroxynaphtha- Ourrant Dark'grey. a) ene- -S 011108101 (quantity correspond ng to 6.9 parts of sodium 2 ammo 5 hydmxynaphtha1ene 7 su1 Du nitrite) 1s added at 5 C. with stirring to the sop o g h h I 1 G G lution of 32 parts of 2-phenylamino-5-hydroxy- -ig gggg mynap t my my bmwn' naphthalene-'l-sulfonic acid and 85 parts of an- -p y y y p t y o v Browlene-G-sulfonic acid.

hydrous sodium carbonate in 1100 parts f water 1 Dyestufi of diazotized aminotriazole Grey violet. Grey olive.

keeping the mixture sodium carbonate alkaline cerboxylie acid with o-fihydroxynaphthalene-T-sulfonic acid during the coupling. The dyestufi isolated in the in acid medium usual Way yields on cotton blue-grey, when a'fter- Dyesgufi d iazotiz i i y fi Violet rey Do. treated with copper salts, dark-grey shades. The .,F. .su1}%$t eh m tl le dyestuil corresponds in the free state to the foldunnlowing formula:

HOsS

| I iI COOH S0311 SOaH l Example 6 Example 7 p The suspension of the diazo compound of the There is prepared a suspension of the diazo dyestuif of the constitution compound of the dyestufi (quantity correspond- C0011 O.CHz.COOH

(quantity corresponding to 6.9 parts of sodium ing to 6.9 parts of sodium nitritelwhich is obnitrite) is added at 5 C. with stirring to the sotained by coupling diazotized aminosalicylic acid lution of 40 parts l-(4'.8'-disu1fo-2-naphthy1)- with 1-aminonaphthalene-G-sulphonic acid, sub- S-methyl-5-pyrazolone and 85 parts of anhydrous sequently diazotizing and coupling with 4-methsodium carbonate in 890 parts of water, keeping y1-2-amino-phenoXy-acetic acid. The suspenthe mixture sodium carbonate alkaline during sion is added at 5 C. with stirring to the soluthe coupling. The dyestuff isolated in the usual tion of 32 parts of 2-phenylamino-5-hydroxyway dyes cotton red-orange, when aftertreated naphthalene-7-sulfonic acid and 25 parts of anwith copper salts reddish-brown shades. The hydrous sodium carbonate in 950 parts of water,

dyestufi corresponds in its free state to the folkeeping the mixture sodium carbonate alkaline lowing formula: during the coupling. The dyestufi isolated in the I $03K CH3 C=N\ I N H O N=NOG o .NH--N=N- N=N -C (IJ I 50311 omcoon The following table indicates the shades of the usual way yields on cotton reddish-blue, when dyestufis which are obtained when the above aftertreatedwith copper salts bluer shades. The

dyestufi corresponds in its free state to the 'following formula:

fooou V omooorr If 2-phenylamino-5-hydroxynaphthalene '7- sulfonic acid is replaced by a. coupling component of the following table dyestufis are obtained which dye cotton shades as indicated If in the diazo compounds mentioned in the beginning of this example the 4-methyl-2-aminophenoxy-acetic acid is replaced by the Z-aminophenoxy-acetic acid, the dyestuffs obtained in the usual way yield on cotton the following shades:

D tr ss Coupling component ig gzg a gg g copper salts 2-amino-5-hydroxynaphthalene-7- Blue violet.-- R e d d i s h sulionic acid. navy blue.

Z-phenylamiuo-fi-hydroxynaphtha- Reddzsh-blue- Blue.

lene-7-sulionic acid.

2-(p-benzoylaminophenylammm-{ido Steel blue.

hygroxynaphthalene 7 sulfomc ac:

Dyestufi of diazotized arninotriazole Blue V i o l e t i s h carboxylic acid with 2-am1nogrey, hydroxynaphthalene 7 sulionic acid in acid medium.

Dyestufi of diazotized ammosahdo Grey.

cylic acid with 2-amino-5-hydroxynaphthalene-'I-sulionic acid in acid medium.

If, however, in the mentioned diazo compound COOH 4-methy1-2-aminophenoxy-acetic acid is replaced by 4-methoxy-2-aminophenoxy-acetic acid, the

dyestuffs obtained in the usual way, yield on cotton the following shades:

D 1 ti d yengon coona r- Couplmg component cotton treated with copper salts Z-amino-E-hydroxynaphthalene-7- Greenish blue. G r e e n 1 s h sulfonic acid. navy blue.

z-phenylamino-fi-hydroxynaphthado Do.

lene-7-sulfonic acid.

Dyestufl oi diazotized aminotria- Blue Dull blue.

zole carboxylic acid with Z-amino- 5-hydroxynaphthalene-7-sulionic acid in acid medium.

Dyestuffs of similar shades are obtained, when the aforementioned coupling components are coupled with the diazo compound of the dyestuff obtained by coupling diazotized aminosulfosalicylic acid with l-aminonaphthalene-G- or 7-sulphonic acid, again diazotizing and coupling with 4-methyl-2-aminophenoxy-acetic acid.

Example 8 The suspension of the diazo compound of the dyestufi of the constitution:

OOH O.CH2.COOH

(quantity corresponding to 6.9 parts of sodium nitrite) is added at 5 C. with stirring to the solution of 37.8parts of the dyestufi obtained by coupling diazotized amino-triazole-carboxylic acid with 2-amino-5-hydroxynaphtha1ene-7- sulfonic acid in acid medium, and parts of anhydrous sodium carbonate in 1500 parts of water, keeping the mixture sodium carbonate alkaline during (the coupling. The dyestuff isolated in the usual manner dyes cotton reddishnavy blue, when aftertreated with copper salts blue-grey shades. The dyestufl" corresponds in its free state to the following formula:

HaC

Example 9 The suspension of the diazo compound of the dyestufi of the constitution:

H20 \C H: N=N N CON: Q

- .omcooH (quantity corresponding to 6.9 parts of sodium of hydroxy-acetic acid and hydroxyrpropionic nitrite) is added at 3 C. with stirring to the acid, R2 stands for one of the group consisting of solution of 32 parts of Z-phenyIaminQ-S-rhythe benzene nucleus, the alkyl-, alkoxyand droxynaphthalene-l-sulfonic acid and parts of tetramethylene-substituted benzene nucleus, and anhydrous sodium carbonate in 1000 parts of 5 R4 stands for a radical of the group consisting water, keeping the mixture sodium carbonate alof coupling components bearing a hydroxy group kaline during the coupling. The dyestufi isoin a position'adjacent to the -N=N bridge lated in the usual way yields on cotton reddishand a 2-amino-5-hydroxynaphtha1ene-7-sulfonic grey, when aftertreated with copper salts, acid substituted in the l-position by an arylazo greenish-dark grey shades. The dyestufi corre- 1O radical whereby at least one of the radicals R1 sponds in its free state to the following formula: and R4 is substituted by an arylazo radical.

CHi-COOH Example 10 a 2. As new products polyazodyestufis of the gen- The suspension of the diazo compound of the 95 em] fommla' dyestuff of the constitution Ha Ha Ri.N=N R: -v N=N-R4 ORa.OO OH wherein R,1 N=N- stands for the residue of a diazo compound derived from aromatic amines GER-000E selected from the group consisting of amines and COOH (quantity corresponding to 6.9 parts of sodium aminoazodyestufis of the benzene and naphtha-v nitrite) is added at 5 C. with stirring to the lene series, 0;.Ra.COO-I-I stands for the radical solution of 32 parts of 2-phenylamino-5-hydroxof a hydroxy carboxylic acid of the group conynaphthalene-"I-sulfonic acid and 25 parts of sisting of hydroxy-acetic acid and hydroxyanhydrous sodium carbonate in 950 parts of 40 propionio acid, R2 Stands One Of group water, keeping the mixture sodium carbonate consisting of the benzene nucleus, the alkyl-, alkaline during the coupling. The dyestufl isoalko-xyand the tetramethylene-substituted benlated in the usual way dyes cotton blue-green, zene nucleus, and R4 stands for the radical of a when afte-rtreated with copper salts, blue-grey 2-amino-5-hydroxynaphthalene-7-sulfonic acid shades. The dyestufi corresponds in its free substituted in the l-pusition by an arylazo radstate to the following'formula: ical.

Ha Ha zH l 1110 on, HO S MPG (30011 7 .omooon I If Z-phenylamino-5-hydr0xynaphthalene7- 3. As new products polyazodyestuffs of the sulfonic acid is replaced by 2-(4='-benzoylaminogeneral formula phenylamino) 5 hydroxynaphthalene-7-su1- fonic acid a dyestufi is obtained, dyeing cotton blue, when aftertreated with copper salts, grey- RFNZN blue shades. 4

We claim: oniooon 1. As new products polyazodyestuii's of the general formula F 60 wherein R.r-N=N- stands for the residue of a diazo compound of an amine of the benzene R N:N series, 0R3.COOH stands for the radical of a hydroxy carboxylic acid of the groupconsisting of hydroxy-acetic acid and hydroxy-propionic wherein R1N=N- stands for the residue of a acid, 2 ds fo o e of the roup co sist n diazo compound derived from aromatic amines 0f the benzene nucleus, the Y- and selemed from t group consigting of aminesand tetramethylene-substituted benzene nucleus, and aminoazodestufis of the benzene and naphtha- 4 Stands f r h ra ical of a 2-amino-5hydroxlene series, O.R3.COOI-I stands for the radical of ap lene-7-sulfomcacid substituted in the 1- a hydroxy carboxylicacid of the group consisting sition y an a yl r al.

1 RaOOOH 4. As new products polyazodyestufis of 'the general formula. V 4

.Rs.COOH

wherein R1-N=N- stands for the residue of a diazoazo compound of an aminoazodystufi of the benzene series, OR3.COOH stands for the radical of a hydroxy carboxylic acid of the group consisting of hydroxy-acetic acid and hydroxypropionic acid, R2 stands for one of the group consisting of the benzene nucleus, the alkyl-, alkoxy-' and tetramethylene-substituted benzene nucleus, and R4 stands for a radical of the group consisting of coupling components bearinga hydroxy group in a position adjacent to 'the -N=N- bridge and a 2-amino-5-hydroxynaphthalene-7-sulfonic acid substituted in the l-position by an arylazo radical. 7

6. As new products polyazodystufis of the general formula oReoooH wherein R1N=NV stands for the residue of a diazo azo compound of an aminoazodyestufi of the benzene series, OR3.COOH stands for the radical of a hydroxy carboxylic acid of the group consisting of hydroxy-acetic acid and hydroxypropionic acid, R2 stands for one of the group consisting of the benzene nucleus, the alkY1 a position adjacent to the -N=N- bridge and a Z amino-5-hydroxy naphthalene-7-sulfonic acid substituted in the 1-position by an arylazo radical.".

8.:As new products polyazodyestufi's oi the generalformula wherein R,1--N=N-- stands for the residue of a diazoazo compound of an aminoazodyestuff one component of which belongs to the benzene series and the other to the naphthalene series, 0R3.COOH stands for the radical of a hydroxy carboxylic acid of the group consisting of hydroxy-acetic acid and hydroxy-propionic acid, R2 standsfor one of the group consisting of the ibenzene'nucleus, the alkyl-, alkoxyand tetraalkoxyand tetramethylene-substitutedbenzene nucleus, and R4 stands for the radical of a 2- amino-5-hydroxynaphthalene '7 sulfonic acid substituted in the 1-position by an arylazoradical.

7. As new products polyazodyestufi's of the general formula wherein R1N=N stands for the residue of a diazoazo compound of an aminoazodystuff one component of which belongs to the benzene series and the other to the naphthalene series, OR3,C00H stands for the radical of a hydroxy carboxylic acid of the group consisting of hydroxy-acetic acid and hydroxy-propionicacid, R2

stands for one of the group consisting of the benzene nucleus,'the a1kyl-, alkoxy-and tetramethylene-substituted benzene nucleus, and R4 stands for a radical'of the group consisting of 7 coupling components bearing a hydroxy group'in methylene-substituted benzene nucleus, and R4 stands for the radical of a. 2-amino-5-hydroxynaphthalene-'Z-sulfonic acid substituted in the 1-position by an arylazo radical.

9. As new products polyazodyestuifs of the general formula Ra.COOH

as claimed in claim 5, wherein the azo portion of R1N=N is 10; new-products polyazodyestuffs of the e mu m a r as claimed claim 6, 'whereinthe azo portion of HOQN=N- 11. As new products polyazodyestufis of the general iormula as claimed in claim 7, wherein the azo portion of -R1'JN N+ is I HOQMF OOH new Products y ye turfs of the general formula as claimed in claim 8, wherein the azo portion of T ill OOH 1 13.;As.:m ew product fthe polyazodyestufi corresponding in its free state to the follcwing formula:

and dyeing cotton grey shades which, when aftertreated with copper salts, show an improved fastness to washing and light.

14. As new product the polyazodyestufi corresponding in its free state to the following for- C Ha E O O C E O.CH2.COOH

and dyeing cotton blue shades which change into greyish-blue shades of improved fastness to washing and light, when aftertreated with copper salts.

15. As new product the polyazodyestufi corresponding in its free state to the following formula:

HO S w G HOQN=N- N=N N= .omcoon and dyeing cotton greenish-blue shades which change into greenish-navy blue shades of im- DETLEF DELFS'. proved fastness to washing and light, when EBERHARD STEIN. aftertreated with copper salts. 

